1. Chapter 16 Preview Objectives Thermochemistry Heat and Temperature
Specific Heat
Enthalpy of Reaction
Enthalpy of Formation
Stability and Enthalpy of Formation
Enthalpy of Combustion
Calculating Enthalpies of Reaction
Determining Enthalpy of Formation

2. Section 1 Thermochemistry
Chapter 16
Objectives
Define temperature and state the units in which it is measured.
Define heat and state its units.
Perform specific-heat calculations.
Explain enthalpy change, enthalpy of reaction, enthalpy of formation, and enthalpy of combustion.
Solve problems involving enthalpies of reaction, enthalpies of formation, and enthalpies of combustion.

3. Chapter 16 Thermochemistry
Section 1 Thermochemistry
Chapter 16
Thermochemistry
Virtually every chemical reaction is accompanied by a change in energy.
Chemical reactions usually either absorb or release energy as heat.
Thermochemistry is the study of the transfers of energy as heat that accompany chemical reactions and physical changes.

4. Chapter 16 Heat and Temperature
Section 1 Thermochemistry
Chapter 16
Heat and Temperature
The energy absorbed or released as heat in a chemical or physical change is measured in a calorimeter.
In one kind of calorimeter, known quantities of reactants are sealed in a reaction chamber that is immersed in a known quantity of water.
Energy given off by the reaction is absorbed by the water, and the temperature change of the water is measured.
From the temperature change of the water, it is possible to calculate the energy as heat given off by the reaction.

5. Heat and Temperature, continued
Section 1 Thermochemistry
Chapter 16
Heat and Temperature, continued
Temperature is a measure of the average kinetic energy of the particles in a sample of matter.
The greater the kinetic energy of the particles in a sample, the hotter it feels.
For calculations in thermochemistry, the Celsius and Kelvin temperature scales are used. Celsius and Kelvin temperatures are related by the following equation.
K = °C

6. Heat and Temperature, continued
Section 1 Thermochemistry
Chapter 16
Heat and Temperature, continued
The amount of energy transferred as heat is usually measured in joules.
A joule is the SI unit of heat as well as all other forms of energy.
Heat can be thought of as the energy transferred between samples of matter because of a difference in their temperatures.
Energy transferred as heat always moves spontaneously from matter at a higher temperature to matter at a lower temperature.

7. Section 1 Thermochemistry
Chapter 16
Specific Heat
The amount of energy transferred as heat during a temperature change depends on the nature of the material changing temperature, and on its mass.
The specific heat of a substance is the amount of energy required to raise the temperature of one gram by one Celsius degree (1°C) or one kelvin (1 K).
The temperature difference as measured in either Celsius degrees or kelvins is the same.

8. Specific Heat, continued
Section 1 Thermochemistry
Chapter 16
Specific Heat, continued
Values of specific heat are usually given in units of joules per gram per Celsius degree, J/(g•°C), or joules per gram per kelvin, J/(g•K).

9. Specific Heat, continued
Section 1 Thermochemistry
Chapter 16
Specific Heat, continued
Specific heat is calculated according to the equation given below.
cp is the specific heat at a given pressure, q is the energy lost or gained, m is the mass of the sample, and ∆T is the difference between the initial and final temperatures.
The above equation can be rearranged to given an equation that can be used to find the quantity of energy gained or lost with a change of temperature.

10. Equation for Specific Heat
Section 1 Thermochemistry
Chapter 16
Equation for Specific Heat
Click below to watch the Visual Concept.
Visual Concept

11. Specific Heat, continued
Section 1 Thermochemistry
Chapter 16
Specific Heat, continued
Sample Problem A
A 4.0 g sample of glass was heated from 274 K to 314 K, a temperature increase of 40. K, and was found to have absorbed 32 J of energy as heat.
a. What is the specific heat of this type of glass?
b. How much energy will the same glass sample
gain when it is heated from 314 K to 344 K?

12. Specific Heat, continued
Section 1 Thermochemistry
Chapter 16
Specific Heat, continued
Sample Problem A Solution
Given: m = 4.0 g
∆T = 40. K
q = 32 J
Unknown: a. cp in J/(g•K)
b. q for ∆T of 314 K → 344 K
Solution: a.

13. Specific Heat, continued
Section 1 Thermochemistry
Chapter 16
Specific Heat, continued
Sample Problem A Solution, continued
Solution: b.

14. Chapter 16 Enthalpy of Reaction
Section 1 Thermochemistry
Chapter 16
Enthalpy of Reaction
The energy absorbed as heat during a chemical reaction at constant pressure is represented by ∆H. H is the symbol for a quantity called enthalpy.
Only changes in enthalpy can be measured. ∆H is read as “change in enthalpy.”
An enthalpy change is the amount of energy absorbed by a system as heat during a process at constant pressure.

15. ∆H = Hproducts – Hreactants
Section 1 Thermochemistry
Chapter 16
Enthalpy of Reaction, continued
Enthalpy change is always the difference between the enthalpies of products and reactants.
∆H = Hproducts – Hreactants
A chemical reaction that releases energy is exothermic, and the energy of the products is less than the energy of the reactants.
example:
2H2(g) + O2(g) → 2H2O(g) kJ

16. Enthalpy of Reaction, continued
Section 1 Thermochemistry
Chapter 16
Enthalpy of Reaction, continued
2H2(g) + O2(g) → 2H2O(g) kJ
The expression above is an example of a thermochemical equation, an equation that includes the quantity of energy released or absorbed as heat during the reaction as written.
Chemical coefficients in a thermochemical equation should be interpreted as numbers of moles and never as numbers of molecules.

17. Enthalpy of Reaction, continued
Section 1 Thermochemistry
Chapter 16
Enthalpy of Reaction, continued
The quantity of energy released is proportional to the quantity of the reactions formed.
Producing twice as much water in the equation shown on the previous slide would require twice as many moles of reactants and would release 2 × kJ of energy as heat.

18. Enthalpy of Reaction, continued
Section 1 Thermochemistry
Chapter 16
Enthalpy of Reaction, continued
In an endothermic reaction, the products have a higher energy than the reactants, and the reaction absorbs energy.
example:
2H2O(g) kJ → 2H2(g) + O2(g)
The physical states of reactants and products must always be included in thermochemical equations, because the states of reactants and products influence the overall amount of energy exchanged.

19. 2H2(g) + O2(g) → 2H2O(g) ∆H = –483.6 kJ
Section 1 Thermochemistry
Chapter 16
Enthalpy of Reaction, continued
Thermochemical equations are usually written by designating a ∆H value rather than writing the energy as a reactant or product.
For an exothermic reaction, ∆H is negative because the system loses energy.
The thermochemical equation for the exothermic reaction previously discussed will look like the following:
2H2(g) + O2(g) → 2H2O(g) ∆H = –483.6 kJ

20. Enthalpy of Reaction, continued
Section 1 Thermochemistry
Chapter 16
Enthalpy of Reaction, continued
In an exothermic reaction, energy is evolved, or given off, during the reaction; ∆H is negative.

21. Enthalpy of Reaction, continued
Section 1 Thermochemistry
Chapter 16
Enthalpy of Reaction, continued
In an endothermic reaction, energy is absorbed; in this case, ∆H is designated as positive.

22. Chapter 16 Enthalpy of Formation
Section 1 Thermochemistry
Chapter 16
Enthalpy of Formation
The molar enthalpy of formation is the enthalpy change that occurs when one mole of a compound is formed from its elements in their standard state at 25°C and 1 atm.
Enthalpies of formation are given for a standard temperature and pressure so that comparisons between compounds are meaningful.
To signify standard states, a 0 sign is added to the enthalpy symbol, and the subscript f indicates a standard enthalpy of formation:

23. Enthalpy of Formation, continued
Section 1 Thermochemistry
Chapter 16
Enthalpy of Formation, continued
Some standard enthalpies of formation are given in the appendix of your book.
Each entry in the table is the enthalpy of formation for the synthesis of one mole of the compound from its elements in their standard states.
The thermochemical equation to accompany an enthalpy of formation shows the formation of one mole of the compound from its elements in their standard states.

24. Stability and Enthalpy of Formation
Section 1 Thermochemistry
Chapter 16
Stability and Enthalpy of Formation
Compounds with a large negative enthalpy of formation are very stable.
example: the of carbon dioxide is –393.5 kJ per mol of gas produced.
Elements in their standard states are defined as having = 0.
This indicates that carbon dioxide is more stable than the elements from which it was formed.

25. Stability and Enthalpy of Formation, continued
Section 1 Thermochemistry
Chapter 16
Stability and Enthalpy of Formation, continued
Compounds with positive values of enthalpies of formation are typically unstable.
example: hydrogen iodide, HI, has a of kJ/mol.
It decomposes at room temperature into violet iodine vapor, I2, and hydrogen, H2.

26. Enthalpy of Combustion
Section 1 Thermochemistry
Chapter 16
Enthalpy of Combustion
The enthalpy change that occurs during the complete combustion of one mole of a substance is called the enthalpy of combustion of the substance.
Enthalpy of combustion is defined in terms of one mole of reactant, whereas the enthalpy of formation is defined in terms of one mole of product.
∆H with a subscripted c, ∆Hc, refers specifically to enthalpy of combustion.

27. Enthalpy of Combustion, continued
Section 1 Thermochemistry
Chapter 16
Enthalpy of Combustion, continued
A combustion calorimeter, shown below, is a common instrument used to determine enthalpies of combustion.

28. Calculating Enthalpies of Reaction
Section 1 Thermochemistry
Chapter 16
Calculating Enthalpies of Reaction
The basis for calculating enthalpies of reaction is known as Hess’s law: the overall enthalpy change in a reaction is equal to the sum of enthalpy changes for the individual steps in the process.
This means that the energy difference between reactants and products is independent of the route taken to get from one to the other.

29. Calculating Enthalpies of Reaction, continued
Section 1 Thermochemistry
Chapter 16
Calculating Enthalpies of Reaction, continued
If you know the reaction enthalpies of individual steps in an overall reaction, you can calculate the overall enthalpy without having to measure it experimentally.
To demonstrate how to apply Hess’s law, we will work through the calculation of the enthalpy of formation for the formation of methane gas, CH4, from its elements, hydrogen gas and solid carbon:
C(s) + 2H2(g) → CH4(g)

30. Calculating Enthalpies of Reaction, continued
Section 1 Thermochemistry
Chapter 16
Calculating Enthalpies of Reaction, continued
The component reactions in this case are the combustion reactions of carbon, hydrogen, and methane:
C(s) + O2(g) → CO2(g)
H2(g) + ½O2(g) → H2O(l)
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)

31. Calculating Enthalpies of Reaction, continued
Section 1 Thermochemistry
Chapter 16
Calculating Enthalpies of Reaction, continued
The overall reaction involves the formation rather than the combustion of methane, so the combustion equation for methane is reversed, and its enthalpy changed from negative to positive:
CO2(g) + 2H2O(l) → CH4(g) + 2O2(g) ∆H0 = kJ

32. Calculating Enthalpies of Reaction, continued
Section 1 Thermochemistry
Chapter 16
Calculating Enthalpies of Reaction, continued
Because 2 moles of water are used as a reactant in the above reaction, 2 moles of water will be needed as a product.
Therefore, the coefficients for the formation of water reaction, as well as its enthalpy, need to be multiplied by 2:
2H2(g) + O2(g) → 2H2O(l)

33. Calculating Enthalpies of Reaction, continued
Section 1 Thermochemistry
Chapter 16
Calculating Enthalpies of Reaction, continued
We are now ready to add the three equations together using Hess’s law to give the enthalpy of formation for methane and the balanced equation.
C(s) + O2(g) → CO2(g)
2H2(g) + O2(g) → 2H2O(l)
CO2(g) + 2H2O(l) → CH4(g) + 2O2(g)
C(s) + 2H2(g) → CH4(g)

34. Calculating Enthalpies of Reaction, continued
Section 1 Thermochemistry
Chapter 16
Calculating Enthalpies of Reaction, continued
Using Hess’s law, any enthalpy of reaction may be calculated using enthalpies of formation for all the substances in the reaction of interest, without knowing anything else about how the reaction occurs.
Mathematically, the overall equation for enthalpy change will be in the form of the following equation:
∆H0 = sum of [( of products) × (mol of products)] – sum of [( of reactants) × (mol of reactants)]

35. Calculating Enthalpies of Reaction, continued
Section 1 Thermochemistry
Chapter 16
Calculating Enthalpies of Reaction, continued
Sample Problem B
Calculate the enthalpy of reaction for the combustion of nitrogen monoxide gas, NO, to form nitrogen dioxide gas, NO2, as given in the following equation.
NO(g) + ½O2(g) → NO2(g)
Use the enthalpy-of-formation data in the appendix. Solve by combining the known thermochemical equations.

36. Calculating Enthalpies of Reaction, continued
Section 1 Thermochemistry
Chapter 16
Calculating Enthalpies of Reaction, continued
Sample Problem B Solution
Given:
Unknown:
Solution:
Using Hess’s law, combine the given thermochemical equations in such a way as to obtain the unknown equation, and its ∆H0 value.

37. Calculating Enthalpies of Reaction, continued
Section 1 Thermochemistry
Chapter 16
Calculating Enthalpies of Reaction, continued
Sample Problem B Solution, continued
The desired equation is:
Reversing the first given reaction and its sign yields the following thermochemical equation:
The other equation should have NO2 as a product, so we can use the second given equation as is:

38. End of Chapter 16 Show